°oA

Q* ^T /

NBS TECHNICAL NOTE 929

^fAU Of

U.S. DEPARTMENT OF COMMERCE/ National Bureau of Standards

A Survey of Current Li

on Sampling, Sample Handling,

and Long Term Storage for

Environmental Materials
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards' was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology

and facilitate their effective application for public benefit. To this end, the Bureau conducts

research and provides: (I) a basis for the Nation's physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology,

the Institute for Computer Sciences and Technology, and the Office for Information Programs.

THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United

States of a complete and consistent system of physical measurement; coordinates that system

with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation's scientific community, industry, and commerce. The Institute consists of the Office of Measurement Services, the Office of Radiation Measurement and the following Center and divisions:

Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Center

for Radiation Research: Nuclear Sciences; Applied Radiation — Laboratory Astrophysics - — Cryogenics" — Electromagnetics -' — Time and Frequency 1'. THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research leading to improved methods of measurement, standards, and data on the properties of well-characterized

materials needed by industry, commerce, educational institutions, and Government; provides

advisory and research services to other Government agencies; and develops, produces, and

distributes standard reference materials. The Institute consists of the Office of Standard

Reference Materials, the Office of Air and Water Measurement, and the following divisions:

Analytical Chemistry — Polymers — Metallurgy — Inorganic Materials — Reactor

Radiation — Physical Chemistry.

THE INSTITUTE FOR APPLIED TECHNOLOGY provides technical services to promote

the use of available technology and to facilitate technological innovation in industry and Government; cooperates with public and private organizations leading to the development of

technological standards (including mandatory safety standards), codes and methods of test; and provides technical advice and services to Government agencies upon request. The Insti- tute consists of the following divisions and Centers: Standards Application and Analysis — Electronic Technology — Center for Consumer

Product Technology: Product Systems Analysis; Product Engineering — Center for Building

Technology: Structures, Materials, and Life Safety; Building Environment; Technical Evaluation and Application — Center for Fire Research: Fire Science: Fire Safety Engineering.

THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts research and provides technical services designed to aid Government agencies in improving cost effec- tiveness in the conduct of their programs through the selection, acquisition, and effective

utilization of automatic data processing equipment; and serves as the principal focus within

the executive branch for the development of Federal standards for automatic data processing

equipment, techniques, and computer languages. The Institute consists of the following

divisions: Computer Services — Systems and Software — Computer Systems Engineering — Information Technology.

THE OFFICE FOR INFORMATION PROGRAMS promotes optimum dissemination and

accessibility of scientific information generated within NBS and other agencies of the Federal Government; promotes the development of the National Standard Reference Data System and

a system of information' analysis centers dealing with the broader aspects of the National Measurement System; provides appropriate services lo»ensurc that the NBS staff has optimum

accessibility to the scientific information of the world. The Office consists of the following

organizational units: Office of Standard Reference Data — Office of Information Activities — Office of Technical

Publications -- Library — Office of International Relations — Office of International Standards.

1 Headquarters and Laboratories u.t (iailhersburg, Maryland, unless otherwise noted; mailing address Washington, DC, 202.14.

- Located at Moulder. Colorado 80302,
Bureau of 'Standards 78

A Survey of Current Literature on Sampling,

Sample Handling, and Long Term Storage

for Environmental Materiais~\e^ A YndVv <v

E. J. Maienthal and D. A. Becker

Analytical Chemistry Division

Institute for Materials Research

National Bureau o( Standards

Washington, D.C. 20234

^T °

F *«

U.S. DEPARTMENT OF COMMERCE, Elliot L Richardson, Secretary

Edward 0. Vetter, Under Secretary

Dr. Betsy Ancker-Johnson, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Acting Director

Issued October 1976
National Bureau of Standards Technical Note 929

Nut. Bur. Stand. (U.S.), Tech. Note 929, 40 pages (Oct. 1976) CODEN: NBTNAE

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1976

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

(Order by SD Catalog No. C13.46:929). Stock No. 003-003- Price 85 cents (Add 25 percent additional for other than U.S. mailing).
A Survey of Current Literature on Sampling, Sample

Handling, and Long Term Storage

for

Environmental Materials

E. J. Maienthal and D. A. Becker

This article is the result of an extensive

literature survey to establish optimum sampling,

sample handling and long term storage techniques

for a wide variety of environmental samples to

retain sample integrity. The components of

interest in these samples are trace elements,

organics, pesticides, radionuclides or microbiologicals. This survey was done both manually

and by use of various bibliographical retrieval

services. Also the advice and opinions of

workers in various aspects of the fields was

obtained

Key words: Environmental samples; long-term

storage; microbiologicals ; organics; pesticides;

sample handling; sampling; chemical analysis; radionuclides; trace elements.

1. Introduction

In order to aid in the development of criteria for the

possible establishment of a National Environmental Specimen

Bank for the Environmental Protection Agency, a large

portion of the recent literature concerning sampling and

storage of environmental specimens has been examined. This

has been done both manually and by use of bibliographical

retrieval services such as Medline, Chemcon, Biosis, Cain,

Defense Documentation Center and others. Also, the advice

and opinion of workers in various aspects of the field has

been obtained. A summary of the results of this survey is

found below, separated into the various areas of concern.

2. Trace Elements

For trace elements there is an abundance of reports on

sampling and storage (which should also apply to radionuclides); however, many of them are contradictory and

should be further resolved by careful experimental work.

Much of the published analytical data apparently is

inaccurate because of such problems as gross sampling contamination or subsequent procedural contamination and failure to make proper blank corrections. Richards states that

some oceanographers have permitted the perpetuation of the
notion that the concentrations of trace elements in the sea

are well known, when, in fact, they are not (1).

Patterson and Settle (2) report that the great mass of

published lead data in plants, animal tissues and water is

in error because of gross positive errors, and that the

relatively large blanks usually present with lead concentrations less than a few ug/g often makes the value obtained

meaningless. Many trace element analysts, particularly in

the field of oceanography and marine biology, believe that

much of the previously published work is unreliable as a result of sample contamination. The values being reported

are progressively lower as techniques are being improved.

Hume reports that if a synthetic sea water were prepared

from the purest reagent chemicals available, it would still

be higher in many trace elements than natural sea water (3)

Whitnack also has evidence to show that the reagents used

are more contaminated than sea water (4). Speecke, e_t al . state that many chances exist for a biological material to

be contaminated before it is analyzed (5) ; but few authors

give the impression of the awareness of this and meaningless

phrases are used, such as "metal-free" containers, "chemically clean" glass, etc., with no evidence to back it up.

Berman states that one must never assume anything is acceptably free from trace metal contaminants until it has been

tested (6)

It is felt that the materials, techniques, and expertise exist to provide viable long-term stored samples for

most trace elements in most matrices; however, few in the

field are using these techniques, partially because as

Boutwell says, "...validity is an expensive commodity" (7).

The first consideration is the choice of the container

and sampler composition and the method of cleaning and

sampling. Murphy, Robertson, Thiers, Patterson, Tolg, and

many others show results which indicate that rubber, neoprene, vycor, polyvinyl chloride, polystyrene, glass, polypropylene, linear polyethylene, platinum, etc., will introduce contamination in sampling and storage (8, 9, 10, 10a,

2, 11). Patterson recommends first, FEP Teflon, then ultrapure quartz, conventional polyethylene or TFE Teflon containers. All cleaning and sample treatment should be done

in laminar flow hoods or a clean room. He recommends cleaning with hot concentrated HN0 3 for three days, rinsing with

high purity distilled water, followed by hot dilute 0.05

percent HN0 3 (both water and acid, prepared as described by

Kuehner, e_t al. (12)) for one day, rinsing and heating with

0.05 percent HN0 3 five days, rinsing, then storing filled

with 0.05 percent HN0 3 , wrapped in cleaned polyethylene

until ready for use. (The two dilute HN0 3 leachings have

T Figures in parentheses indicate the literature references on page 16.

2
not been found necessary by some other workers) . When ready

for use, the containers can be thoroughly rinsed and dried

in laminar flow hoods. Cleaned plastic gloves are worn in

all phases of cleaning, sampling, etc. (2). Berman found

that even after thorough cleaning and scrubbing of fingers,

0.1 to 0.4 ug of lead could still be washed off. Washings

from a chain smoker give results of 0.3-4 yg of lead (6).

Karin, et_ al. report a three-day leach of polyethylene ' in either 8 or 16 M HN0 3 was necessary to remove certain

trace metal contaminants (13)

.

Sampling implements Patterson recommends are either

Teflon or Teflon-encased, except for frozen tissue sampling

where a series of HN0 3 -acid cleaned stainless steel blades

are used with very elaborate sampling procedures to remove

areas contaminated by the blade (2) . All of these type

operations should be done in laminar flow hoods or clean

room conditions.

Deionized water which has not been followed by distillation should not be used in any stages of the cleaning,

sampling, or analysis as organic breakdown products may be

formed, complexing some of the trace elements (8).

Numerous types of water samplers have been devised.

Segar, e_t al. have described water sampling with Niskin

bottles with rubber coated springs, Teflon coated coil

springs and a new design Niskin bottle without internal

closures. All gave trace metal contamination except the

latter (14). Since Teflon is rather porous, apparently some

metal diffusion through the spring coating must have

occurred

.

Harrison, e_t al. have designed a Teflon cylindrical

sampler with a mechanism for opening both ends after submersion to the desired depth to avoid contamination from the

water surface (15) . It is attached to a metal frame and

rudder which have a baked-on Teflon coating. It is also

adapted so that the sample may be filtered immediately in an

attached container holding a precleaned polyethylene bag in

which the sample can be immediately sealed and frozen in

liquid nitrogen. If the water sample is to be filtered,

Morrison and Pierce, and many others suggest that it is best

to do it immediately (16) . The filter must be thoroughly

precleaned, rinsed, and stored in cleaned polyethylene bags.

The sample chamber used by Patterson (2) consists of

accordion pleated Teflon tubing, the entry port being protected by a bath of ultra pure water (prepared as already

mentioned). At the deep water sampling depth desired, a
trigger retracts the water bath shroud and ruptures the end

diaphragm which contains the pure water. The water sampler

is lowered continuously so that it is continually dropping

into virgin water. After a short interval to allow the bath

water to be washed away, a second trigger expands the sample

accordion bag and seals the entry port.

The storage of aqueous samples presents an even greater

challenge as most samples start undergoing changes the

instant they are sampled. Pre-aging the sampler and sample

container with some of the same sample would be desirable

whenever possible. Amore states that losses as high as 50

percent can occur during one hour of storage (17) . An EPA

manual on methods of water analysis says that complete and

unequivocal preservation of samples is a practical impossibility, that complete stability can never be obtained, and

that preservation techniques only retard the chemical and

biological changes that continue after the sample is taken

(18) . The methods of preservation are intended to retard

biological action, retard hydrolysis of chemical compounds

and reduce the volatility of the components. Their recommended methods include pH control, chemical addition,

refrigeration, and freezing.

Although there is much in the literature on relatively

short term storage of different aqueous (non-frozen) solutions under varying conditions, there are many disagreements

and most of the results do not look favorable for long term

storage. A USGS manual for water analysis says that the

shorter the time that elapses between the collection of a sample and its analysis, the more reliable will be the

results (19)

Pettis and Phillip give an excellent review of the

literature on trace metal analysis in sea water. They

discuss sampling and cleaning procedures, sample pretreatment, standard reference materials, and analytical method of

determination of the trace metals (19a)

Robertson found that sea water adjusted to pH 8 stored

in polyethylene resulted in a 90 percent indium loss in 20

days and a 90 percent loss of iron in 55 days (20) . Hummel

found that 75 percent of the gold in sea water was lost

after three weeks in polyethylene (21). King, e_t al. found

that less than 3 percent of the cadmium was lost to polyethylene at pH's of 3 to 10 after two weeks storage (22).

West, e_t a_l. (23) found more silver adsorption on glass at

pH 4 than at pH 7, a significant decrease occurring at pH 7,

and a rise at pH 8, and they also state that pyrex showed

more erratic adsorption patterns than polyethylene or silicone-coated containers. Struempler (24) states that acidi-
fication with nitric acid to pH 2 prevents adsorption of

silver, lead, cadmium, and zinc on pyrex, and silver on

polyethylene. Dyck (25) reports lack of confirmation with

the work of West, et a_l. with silver, and states there is a direct increase in silver adsorbed on glass with increase in

pH. He also states that for periods over several months,

plastic adsorbed more silver than glass. Lai and Weiss (26)

found no silver loss when sea water was stored in polyethylene and acidified to a pH of 3 . 5 to 4 . with acetic

acid. King, et a_l. (22) found losses as high as 75 percent

for cadmium wEen stored in glass at pH 9. Eichholz, et al . (27) compared adsorption of a number of elements on pyrex

and polyethylene and state that pyrex is preferable to

polyethylene; however, they found less contamination for

cesium, ruthenium, and zirconium when using polyethylene.

Smith (28) studied stability of a number of ions including

cadmium, antimony, tin, and lithium, and states that of the

elements studied only lithium was stable over the pH range

of one to 11. He therefore recommends acidification to pH

one. In another report (29), he states that freezing the

liquid samples as soon as they are collected is an excellent

solution for the adorption problem. The losses may be due

to adsorption or also to precipitation or particulate formation. Salman also states that freezing can be used to

preserve the water samples at the collection site (29a)

.

Rattonetti examined the stability of a large number of

trace metals in a variety of water matrices stored in polyethylene at differing pH ? s and concluded that loss to container walls is insignificant compared to losses to the

particles present in natural aqueous systems (30)

.

Moody, e_t al. prepared two mercury- in-water Standard

Reference Materials at the 1 ppm and 1 ppb level which have

been stable for over a year in both glass and polyethylene

(31) . This was achieved by the addition of 1 yg/g and

10 ng/g of Au+3

, respectively, and 0.5 N nitric acid. Lo

and Wai verified this for shorter term storage with 0.2

yg/g Au +3 and nitric acid at pH 0.5 (32), but were unable

to confirm Feldman's stabilization with potassium dichromate

(33) or the report of Issaq and Zielinski with hydrogen

peroxide (34) . Avotins and Jenne state that the biological

effects have been overlooked in many mercury in water investigations, and as a result of unpredictable growth of bacterial and yeast populations, with production of metabolites,

mercury may either vaporize, bind to the walls of the vessel

or be stabilized in solution (35) . Huey, e_t al. have

reported that cadmium can be volatilized from its inorganic

salts by a microorganism through conversion to a volatile

organic compound (36). The volatilization is stimulated by

vitamin Bi 2 . Methylmercury formation by this organism is
also stimulated by B 12 , the absence of which causes the

organism to form metallic mercury from inorganic mercuric

salts. In samples where this type of reaction occurs,

freeze-drying is not advisable as a method of sample preservation. For long term preservation for trace-element

analysis, freezing and possibly freeze-drying for most

elements (probably followed by radiosterilization) , would

seem to be the most likely alternatives. Morrison and

Pierce state that freezing may be a suitable preservation

technique for trace elements but has not been adequately

tested to date (16) . Allen, e_t a_l. recommend immediate

freezing at -10 to -15°C to prevent microbiological changes

in soluble mineral and silica concentrations (37); however,

for long term storage, immediate freezing in liquid nitrogen

as recommended by Harrison, ejt a_l. (15) and others (29) , followed by freeze-drying for most trace elements (and

radiosterilization) or storage at -70° to -80°C would seem

preferable. Low temperature (oxygen plasma) ashing and dry

ashing are also possibilities in some cases.

Harrison, ejt aJ. (38) and Filby, e_t a_l. (38a) , have

reported that radioisotope studies of the volatile elements

such as arsenic, antimony, selenium, bromide, and mercury

have shown no significant losses in water samples which have

been freeze-dried.

Heron studied the determination of phosphate in lake

water before and after freezing (39) . It was expected that

rapid freezing would cause cell rupture resulting in higher

phosphate values, but this did not occur. Varying phosphate

values were found whenever growth of bacteria was occurring.

This was prevented by pre-cleaning the sample bottle with a solution which is 5 percent in iodine and 8 percent in

potassium iodide and immediate freezing of the water sample.

Philbert found that in freezing lake water samples

soluble reactive silica and phosphorus concentrations were

decreased in the thawed samples (40) . A decrease in total

alkalinity and dissolved chloride was also observed.

Inconsistent changes were observed for ammonia and the

various forms of nitrogen.

A USGS manual on methods of water sampling recommends

that water samples for inorganic analysis should not be

frozen (19); however, there is sufficient reason to expect

that if the process is performed properly, freezing is

acceptable for most trace elements. The samples should be

subsampled before freezing, because once thawed, they should

not be refrozen. The entire subsample should then be taken

for analysis. They should be frozen in one of the container

materials already discussed, under a gas such as nitrogen or
argon to prevent sample oxidation. They should be sealed in

at least 2 and possibly 3 [as Patterson recommends (2)]

series of plastic bags. Since most plastics are porous

(41) , they should then be placed in a tightly sealed glass

container containing nitrogen or argon with minimum void

space, followed by storage in the dark at -70°C. Bothner

and Robertson (42) have reported that sea water samples

stored in polyethylene containers have picked up mercury

from being stored in a room contaminated with metallic

mercury. This has been verified in a closed chamber with

pools of clean mercury surrounding a mercury solution in

Teflon and polyethylene bottles, but has not as yet been

verified in an ordinary laboratory atmosphere where spilled

mercury would probably be covered with dust, thus effectively

diminishing its vapor pressure (43)

.

When the frozen water sample is used, the whole sample

should be used because of possible selective ion incorporation

in the ice (44) . The walls of the inner container will

probably have to be washed with acid to remove any hydrolyzed

or adsorbed material.

The possibility of losing organic or inorganic mercury

during freeze-drying of biological materials was investigated

by LaFleur, as Pillay, et_ al. had published data indicating

losses (45) . LaFleur found no losses for inorganic or

naturally bound methyl- or phenylmercury in tissue and

blood; however, for aqueous solutions, losses of up to 90

percent could occur for organic and up to 10 percent for

metallic mercury (46)

.

3. Biological-Tissue and Fluids

For tissue and biological fluid sampling, the sampling

device presents considerably more difficulties. The use of

a laser beam for cutting bone by Hislop and Parker (47)

offers many interesting possibilities. Some loss of trace

elements on the surface may occur but would be negligible

with regard to the entire sample. A quartz or glass knife

should also be suitable for many kinds of tissue. Montgomery,

et al. used a glass knife to cut fish in small pieces for

the"~a

retermination of iron, zinc, lead, cadmium, copper, and

manganese (48) . A problem here is the chipping of the

cutting edge; weighing the knife before and after use may

indicate if this difficulty arises.

Most workers use stainless steel implements. However,

this is frought with dangers of contamination for many trace

elements even when done as carefully as described by Patterson

earlier (2) . Versieck, et al. report on the contamination

introduced during needle biopsies of liver (49) . They state

that steel surgical blades lead to somewhat less contamination,

7
but are not suitable for some trace elements such as chromium and nickel. The needle biopsies resulted in contaminations of as much as 1.7 ppm of copper, 0.64 ppm of manganese, 11 ppm of chromium, 12 ppm of nickel, 20 ppm of

iron, 0.24 ppm of cobalt, 0.012 ppm of silver, 0.46 ppm of

tin, 0.069 ppm of antimony and 1.2 ppm of tantalum. Speecke,

et al . have reported on the sampling and storage of biological materials for contamination by chromium, manganese,

nickel and cobalt by drawing 4 series of 20 ml portions of

blood using disposable needles (5). For manganese, the

first 20 ml showed contamination of 0.2 ppb, the fourth,

0.02 ppb; for chromium, the first 85 ppb, the fourth 15 ppb;

for nickel, the first 71 ppb, the fourth 12 ppb; for cobalt

the first 0.9 ppb, and the fourth 0.2 ppb. They also compared contamination introduced in another series of liver

samples using Meneghini biopsy needles and surgical blades.

For the needles, they found contaminations of as much as 600

ppb of manganese, 9000 ppb of chromium, 12,000 ppb of nickel

and 230 ppb of cobalt; for the surgical blades, 3 ppb of

manganese, 15 ppb of chromium, 60 ppb of nickel, and 1 ppb

of cobalt. They discuss the possibility of using laser

beams on hard and soft tissues and platinum-rhodium alloy

needles; however, it is preferable that the platinum needles

have Kel-F hubs to avoid contamination. For storage,

Speecke, et_ al. recommend immediate, rapid freeze-drying

,

but point out that some volatile materials may be lost. All

the work should be done in a clean-room type laboratory with

no exposed metal parts which might cause contamination.

Fisher, et_ a_l. (50) also reported that serum samples

should be quickly frozen with as little air space as possible

(as described earlier, the air should be displaced with

nitrogen or argon) . They also checked storage at room

temperature, 8°C and -15°C. No differences for calcium,

magnesium, copper, zinc, sodium, and potassium were noticed

up to 16 days. Essentially no changes were observed in the

refrigerated and frozen samples up to 50 days, but changes

did occur in the samples stored at room temperature.

Longer term storage would probably also result in changes in

the refrigerated samples. Some microorganisms can grow in a temperature as low as -6°C (51)

In a discussion of sampling for clinical chemistry,

Ibbott recommends separating the serum from the clot as soon

as possible to avoid contamination from cell leakage (52)

He also states that the majority of the serum components are

stable indefinitely in dry ice (about -70°C), and that the

samples exhibit concentration gradients due to freezing and

must be thoroughly mixed after thawing. Omang and Vellar

also point out the concentration gradients obtained after

freezing and thawing serum, sweat, and urine. They found

top-bottom differences of thawed samples of up to one

hundred (53)

8
4. Museum Specimens

The futility of trace element analysis of museum type

specimens stored in preservatives has been pointed out by a number of authors. Bowen and Sutton in analysis of marine

sponges found that nickel accumulation in the preservative

occurs quite frequently in these types of samples (54)

.

Gibbs, et al. investigated the effects of time and preservatives on museum fish specimens and found no evidence to

support the theory that preserved museum specimens can

provide reliable estimates of heavy metal concentrations

(55) . They tested many types of preservatives such as

ethanol, formalin, isopropyl alcohol, etc., and found interaction with the specimens in all cases. These solvents may

either leach trace metals from the specimen or contaminate

the specimens by heavy metals contained in the preservatives

or container. In many cases, metal identification tags are

placed in with the preservative, which contribute even

further to the contamination of the sample. In some instances,

the trace metal content increased over the years and in

other cases, decreased from leaching even in a short period

of time, such as a month.

A possible exception for the museum type specimens are

those which have been stored in relatively clean, dry areas

not subject to leaching or contamination. Cockburn, e_t al . (56) describe the autopsy of an Egyptian mummy, Pum II,

which included the analysis of some trace elements in bone

by R. G. Smith (57). He found 0.6 ppm of lead and 0.43 ppm

of mercury. The lead content of modern bone averages 6.55

to 18 ppm (58). Assuming no leaching has occurred, it would

appear, on the basis of limited sampling, that man's environment has contributed considerably to his lead body burden.

The mercury level, however, is relatively unchanged, that of

modern bone averaging about 0.45 ppm (59).

5. Crustal and Botanical Materials

The sampling and storage of soils, rocks, minerals,

sediments, and plants does not present quite as many problems as the matrices already discussed, but more precautions

should be taken then are generally observed. Morrison and

Pierce (16) state that the use of a spade to sample soil is

preferable to a soil auger and. that dry samples can be

collected in a clean cloth bag, but this procedure would

certainly lead to contamination for some trace metals.

Clean Teflon encased tools as recommended by Patterson and

Settle (2) should be used except for most plants which can

be picked with clean plastic gloves. It appears that soils

and sediments with any significant water content (especially

sediment samples) should be frozen in such a way that no

water loss can occur, and stored as recommended for water

samples

.

9
There are many papers in the literature which indicate

that soils and sediments undergo changes in structure and

chemical state even when dried at room temperature. This

should not have a great effect on the total trace element

content in most cases, but if speciation, organic extractable trace elements, etc., are of interest, any form of

drying may invalidate the sample. Attoe (60) reports that

potassium may be fixed in a nonexchangeable form when a potassium-fertilized soil is air-dried. Air drying of

unfertilized soils resulted in a 4-90 percent increase in

exchangeable potassium when the soils are remoistened.

Schalsha, et_ al. (61) state that air drying produces significant irreversible changes in volcanic ash soils. For

instance, soil samples with a clay-type texture in the

field, change to a sandy texture with air drying. Air

drying also reportedly markedly affects cation exchange

capacity, soluble phosphorus and iron, and decreases the pH

slightly. Air drying decreased the total exchangeable and

acid soluble iron, but increased the chelatable iron

extracted by salicylate. The mechanical and chemical

analysis of volcanic ash soils more accurately indicate

field conditions when samples contain the original moisture

at field capacity.

Barrow (62) found when soils were dried, inorganic

sulfate immediately increased (probably as a result of

decomposing organic sulfates in the soil becoming immediately available to the plants) . Even when two different

soils are dried at the same temperature, the relative

availability of the sulfur may be no indication of the

relative availability when they were fresh.

Harpstead and Brage (63) reported that the drying and

storage of soils leads to a pronounced increase in their

nitrifying ability because of the changes in the relative

numbers of various microorganisms in the soil. Birch found

that when remoistening dried soil, the first rapid decomposition slows down and this pattern is repeated during

successive dryings and wettings (64) . The magnitude of the

decomposition depends on the amount of carbon in the soil

and on the drying conditions, air drying being less effective than oven drying. Vacuum drying and oven drying gave

the same moisture loss results, but oven drying gave a much

greater amount of decomposition on rewetting.

Birch (65,66) also states that the longer a soil is

kept air dried, the greater the amount of water-soluble and

organic material that can be extracted, even though it does

not lose additional moisture, and also the greater the

amounts of carbon and nitrogen are mineralized on remoisten

ing . He also finds greater effects if the soil is dried at

100°C, possibly because of increased gel porosity and

10
surface area, and possibly because of increased microbiological activity occurring during the remoistening of the

dried soil.

Nevo and Hagin (67) state that the changes occurring

after three months of air drying storage was independent of

microorganisms. The major factor is the change in the

physical structure of the organic fraction. They found a good correlation between the nitrification rate and the

surface area of particles of an organic soil.

Hesse (68) states that oven drying a soil, despite its

reproducibility, should not be recommended, because of the

profound changes caused. Also he says that storing a soil

in a moist state has the effect of incubating it, but without temperature or moisture control, resulting in a build-up

of carbon dioxide at the expense of oxygen. As such treatment results in many complicated reactions, it is most

undesirable to keep a soil in a moist state for any length

of time for the purpose of analysis. He also reports on

investigations of J. M. Coleman (private communication) that

moist soil samples stored in plastic containers can result

in fundamental changes in clay minerals. It is thought that

an organic complex passes from plastic into the clay mineral

All these references seem to point out that drying or

freeze-drying may result in irreversible changes which will

affect also the complexation state of the trace metals and

that freezing at -70°C to -80°C as recommended earlier

should be the method of storage.

Plant sampling can probably be done by picking with

plastic gloves and storing by freezing in containers as

already mentioned, with care to avoid moisture loss.

Arkeley, et al. (69) state that trace elements such as

carried by peat dust deposited on plants are easily washed

off (high purity distilled water should be used) but those

deposited by sprays are not, because of partial absorption

in the leaf. Lagerwerff (70) found increases in absorption

of cadmium, zinc, and lead on leaf surfaces probably

enhanced by drying.

Work by Koeppe and Miller (71) showed a much higher

uptake of lead by maize roots than in the stems or leaves.

Washing with distilled water removed little lead, but washing with EDTA solution removed about 90 percent of the lead,

indicating the lead is largely retained on the exterior

surface of the roots.

For sampling of air particulates, Patterson and Settle

(2) recommend cleaning Millipore or Nucleopore filters by

soaking in cold 6N HC1 two days, rinsing on a cleaned

11
polyethylene Buchner funnel with high purity distilled

water, soaking two days at 55°C with 1 percent NHi+F (prepared by neutralizing high purity NH^OH with high purity HF)

followed by rinsing with high purity water. These operations, of course, are carried out in a clean room atmosphere

or laminar flow hoods. The filters are then stored in

cleaned polyethylene bags or boxes. The lead blank on

these filters was found to be less than 1 ng/47 mm filter.

6. Organics and Pesticides

With the exception of the use of plastic gloves for

sampling to avoid contamination from body oils (72) , storage

containers and implements for trace orgartics and pesticides

definitely must not be plastic of any kind, with the possible

exception of Teflon, as plastic is known to both introduce

interferences and sorb pesticides (and organics) (73,73a).

Many examples are given in the literature which show that

additives such as plasticizers , organometallic or other

stabilizer antioxidants, colorants or other components are

leached from the plastic and contaminate the sample (74)

Some polyvinyl chloride tubings were shown to release a constituent to some systems containing alcohol, propylene

glycol or polyethylene glycols (75) . Gibbs found that

asbestos fiber was highly contaminated by 3 , 3 ' - 5 , 5 ' -tetratertiary butyl diphenoquinone after storage in polyethylene

bags (76) . Lipids in soil samples stored in standard plastic

lined canvas bags were found to take up phthalate esters and

other contaminants from the plastic (77)

Most workers in the field recommend storage in glass

containers with Teflon or aluminum foil lined caps (72,73,

73a, 78); however, it has been reported that Teflon sheet and

aluminum foil have been found to contain up to 400 and 300

ppb, respectively, of di-2 ethylbutyl phthalate (79,80).

Hertz, et al. (81) recommended cleaning the glassware

with soap andwater, then in concentrated HaSOi; at 100°C

for 30 min and finally rinsing with specially prepared

distilled water made by redistilling the house distilled

water over KMn0 4 -K0H. The distillate is then passed through

an XAD-2 column, and the water is redistilled to remove any

particulates from the XAD-2 resin. Finally, the bottles are

then rinsed with methanol and triple-distilled pentane, and

filled with nitrogen from a liquid nitrogen source and

sealed.

Others recommend wrapping the cleaned glassware in

aluminum foil and heating at 625°C for four hours (82) . The

maintenance of high quality distilled water can be a problem

as some microorganisms can grow rapidly in distilled water

12
and some chemical reagents (82,83,84). It is reported by

Hamilton and Myoda (82) that the amino acids, proteins and

bacteria often found in some laboratory reagent solutions

and distilled water, are probably airborne and enter the

outlet of the stills or deionizing systems where they

multiply. A method of catalytic pyrodistillation has been

reported to remove organic impurities not removed by ordinary or oxidative distillation because of the steam volatility of the compounds or their derivatives (85).

It has been recommended in sampling that "an analyst or

person directly concerned with the particular study should

collect the samples. Inexperienced personnel should never

be allowed to collect the samples unless they are very

closely supervised" (78). This, of course, is true to all

types of environmental sampling.

When sampling marine organisms and sediments for organics

or pesticides, most workers recommend freezing immediately

in dry ice or liquid nitrogen (72,81) and final storage at

about -70° to -80°C (86) in the dark. Breakdown of pp'-DDT

to pp'-TDE in Bengalese finch liver, and breakdown due to

other biological processes have been reported at home

freezer storage conditions (approximately -14°C) (87,88).

Bristol reported in a study of pesticide residues in

potatoes that metabolically incorporated 2,4-D untreated

potato samples stored whole at 4°C decreased over a period

of 15 months, while those of 2,4-DCP remained constant.

Recoveries of 2,4-D from frozen samples were constant over a 15-month period, but those of 2,4-DCP decreased slowly from

88 to 47 percent. The 2,4-DCP samples stored in plastic

bags gave a characteristic odor, indicating the losses were

due to volatilization from the frozen samples (89)

.

It is reported by the Federal Working Group on Pest

Management that increased knowledge of sample contact with

various kinds of synthetic wraps and containers demonstrates

the necessity for glass and perhaps aluminum foil to preserve

the integrity of wet samples. Immediate freezing and maintenance of the frozen sample until analysis is the best way

to protect samples and prevent degradation and loss of

pesticide residues (73) . (This also is undoubtedly true for

all organic components.) They also state that pesticides

can migrate to the walls of a container and be adsorbed;

hence, even with a glass container, after the sample is

poured out, the walls should be rinsed with the solvent in

case the extraction is not made in the container itself

(this should also apply to any organics)

.

There is evidence in the literature that samples to be

analyzed for organics or pesticides cannot be dried or

13
freeze-dried without danger of some loss. One study showed

79 percent loss of lindane, 37 percent for dieldrin, 57

percent for p,p'-DDT and 31 percent in o,p'-DDT-DDD on whole

eggs and 50 percent for lindane in egg yolk when samples

were frozen at -23°C, freeze-dried for 24 hr, and transferred and stored in sealed glass vials at 4°C, so that

there was no volatility loss in storage (90)

Morris found that preservation of zooplankton in

formalin and methanol resulted in hydrolysis of the animals'

lipid and degradation of polyunsaturated fatty acids (90a)

He found that the samples were stable up to nine months if

stored deep frozen under nitrogen.

Smith reports that changes in nonstructural carbohydrate concentrations occur during the storage of either

heat or freeze-dried tissues and concluded that no preservation method is as good as the immediate analysis of fresh

tissue; however, he did not investigate straight freezing

(91) . Other workers found losses in higher fatty acids

under either oven or freeze-drying conditions after storage

for nine months (92)

Dessicants for tissue preservation are used by some

workers who are unable to freeze their samples. The samples

are chilled, homogenized, and blended with a combination of

sodium sulfate and powdered silica. It is stated that the

resulting mixture is a dry, free-flowing powder wherein the

pesticide residues are stable for 15 days or more at room

temperature (73)

7. Microbiologicals

Microbiologicals or cellular organisms consist of many

different types such as algae, protozoa, fungi (molds or

yeasts), bacteria, submicroscopic viruses and other (microscopic nematodes, some insects and some crustaceans),

necessitating a wide variety of different sampling and

storage conditions. Most preservation has been done through

culturing and subculturing . With care, these have been

maintained for 5-8 years (93). The sampling implements and

containers should obviously be sterile and glass is preferred

to plastic, since bacteria tends to grow on plastic surfaces.

Since all known life forms require water in the liquid

state, this automatically limits the temperature range for

microorganisms. Both bacteria and viruses can be freezedried to maintain culture collections and to preserve them

for use as vaccines. Insects have been supercooled to -30°C

without apparent damage; however, they die if ice crystals

are formed. Mouse embryos have survived deep freezing to - 196°C. Freezing is accompanied by the removal of water, so the cell is subject to damage by both freezing and drying.

14
Mechanical injury is caused by ice crystals and the removal

of the water causes an increase in dissolved substances.

Biochemically debilitated cells may show a reduction or

complete loss of some enzymes, and ice-damaged cells may

have leaky membranes or an altered structure. The damage

from freezing, drying, and thawing can range from essentially

none to 100 percent, depending on the specific organism and

conditions. Spores are resistant to both cold and drying.

Rapid freezing is reported to be usually better with bacteria, whereas slow freezing is better for animal cell

survival. It has been stated that rapid thawing gives

better survival than slow thawing (51) . Fleischer and

Kervina report in studies on long-term preservation of liver

for subcellular fractionation that rapid freezing and thawing minimizes the time in which degradation can occur (94)

.

Repeated freezing and thawing is more harmful. Freeze-dried

bacteria are better kept at refrigerator temperature than at

room temperature (51)

.

McPeak and Camp (94a) have reported on work of Valeri,

et al. (95) , Meryman and Hornblower (96) , and Gibson, ejt al . (97) . Their studies on storage of red blood cells show that

if the samples are stored at a higher temperature than - 60°C, they deteriorate within a few weeks. If glycerol is

used as a cryoprotective agent and the cells are frozen

rapidly in liquid nitrogen and stored at -80°C, the cells

are reported to be stable for over 10 years. Fluctuations

in storage temperatures of not more than 10°C above or

below -80°C are reported to have no adverse effect. Farrant,

et al. (98) report that improved recovery of frozen cells

can^b"e obtained by interrupting rapid cooling with a timed

exposure to a single subzero temperature.

There is a vast amount of additional information in the

literature on the subjects of sampling, handling, and storage for microbiologicals , blood, and other biological

samples. Since there are so many different types of species

and the related optimum handling appropriate to each specie,

it is difficult to summarize; however, a number of additional references are given below to indicate the type of

problems that are encountered as well as some additional

references concerning other subjects discussed above.

15
References

1. F. A. Richards, On the State of Our Knowledge of

Trace Elements in the Ocean, Geochim. Cosmochim Acta,

10, 241-243 (1950).

2. C. C. Patterson and D. M. Settle, The Reduction of

Orders of Magnitude Errors in Lead Analyses of Biological Materials and Natural Waters by Evaluating and

Controlling the Extent and Sources of Industrial Lead

Contamination Introduced During Sample Collecting,

Handling, and Analysis, NBS, TS.*

3. D. N. Hume, "Pitfalls in the Determination of Environmental Trace Metals," in Progress in Analytical Chem-

.istry, Vol. V, Ed. S. Ahuja, E. M. Cohen, T. J. Kneip,

J. L. Lambert, and Gunter Zweig, pp. 3-16, Plenum Press,

New York, London (1973).

4. G. C. Whitnack, Application of Single-Sweep Polarography

to the Analyses of Trace Elements in Sea Water,

Polarography, 641-651 (1964).

5. A. Speecke, J. Hoste, and J. Versieck, Sampling of

Biological Materials, NBS, TS.*

6. E. Berman, The Challenge of Getting the Lead Out, NBS,

TS.*

7. J. H. Boutwell, Jr., Accuracy and Quality Control in

Trace Element Analysis, NBS, TS.*

8. T. J. Murphy, The Role of the Analytical Blank in

Accurate Trace Analysis, NBS, TS.*

9. D. E. Robertson, Role of Contamination in Trace Element

Analysis of Sea Water, Anal. Chem. , 4_0, 1067-1072 (1968)

10. R. E. Thiers, Separation, Concentration and Contaminatioi

in Trace Analysis, Ed. J. H. Yoe and H. J. Koch, Jr.,

pp. 637-666, Wiley, New York (1957).

10a. R. E. Thiers, Contamination in Trace Element Analysis

and Its Control in Methods of Biochemical Analysis, Ed.,

D. Glick, Vol. V, pp. 273-333, Interscience Inc.,

New York (1957)

11. G. Tolg, Extreme Trace Analysis of the Elements-I,

Methods and Problems of Sample Treatment Separation and

Enrichment, Talanta, 1£, 1489-1521 (1972).

16
12. E. C. Kuehner, R. Alvarez, P. J. Paulsen, and

T. J. Murphy, Production and Analysis of Special HighPurity Acids Prepared by Sub-Boiling Distillation,

Anal. Chem., 44, 2050-2056 (1972).

13. R. W. Karin, J. A. Buono, and J. L. Fasching, Removal

of Trace Elemental Impurities from Polyethylene by Nitric

Acid, Anal. Chem., 47, 2296-2299 (1975).

14. D. A. Segar and G. A. Berberian, Comparisons of Sample

Contamination by Pumping Systems, Niskin Bottles with

Rubber and Teflon Coated Coil Springs, and New

Niskin Bottles Without Internal Closures, Paper presented

at the 168th ACS National Meeting held in Atlantic City,

N. J. , September 1974.

15. S. H. Harrison, P. D. LaFleur, and W. Zoller, Sampling

and Sample Handling for Activation Analysis of River

Water, NBS, TS.*

16. G. H. Morrison and J. 0. Pierce, Sampling, Sample

Preparation and Storage for Analysis, in Geochemistry and

the Environment, Vol. I, pp. 90-97, National Academy

of Sciences, Washington, D. C. (1974).

17. F. Amore, Losses, Interferences and Contamination in

Trace Metal Analysis - Some Examples, NBS, TS .

18. U. S. Environmental Protection Agency, Methods for

Chemical Analysis of Water and Wastes, p. VI, Office

of Technology Transfer, EPA (1974).

19. Federal Interagency Work Group on Designation of Standards

for Water Data Acquisition, Recommended Methods for Water

Data Acquisition, p. V-10, U. S. Department of the

Interior, Geological Survey, Office of Water Data

Acquisition (1972)

.

19a. R. W. Pettis and A. T. Phillip, Trace Analysis of Heavy

Metals in the Marine Environment, Rept. 619, Australian

Defence Scientific Service, Materials Research Laboratories, Maribyrnong, Victoria, December 1974.

20. D. E. Robertson, The Adsorption of Trace Elements in

Sea Water on Various Container Surfaces, Anal. Chim.

Acta, 4_2, 533-536 (1968).

21. R. W. Hummel, Determination of Gold in Sea Water by

Radioactivation Analysis, Analyst, 82, 483-488 (1957).

17
22. W. G. King, J. M. Rodriguez, C. M. Wai, Losses of Trace

Concentrations of Cadmium from Aqueous Solution during

Storage in Glass Containers, Anal. Chem. , 4_6, 771-773

(1974)

23. F. K. West, P. W. West, and F. A. Iddings, Adsorption

of Traces of Silver on Container Surfaces, Anal. Chem.,

38, 1566-1570 (1966).

24. A. W. Struempler, Adsorption Characteristics of Silver,

Lead, Cadmium, Zinc, and Nickel on Borosilicate Glass,

Polyethylene, and Polypropylene Container Surfaces,

Anal. Chem., 4_5, 2251-2254 (1973):

25. W. Dyck, Adsorption of Silver on Borosilicate GlassEffect of pH and Time, Anal. Chem., 4_0, 454-455 (1968).

26. M. G. Lai and H. V. Weiss, Determination of Silver in

Sea Water, Anal. Chem., 34, 1012-1015 (1962).

27. G. G. Eichholz, A. E. Nagel, and R. B. Hughes, Adsorption of Ions in Dilute Aqueous Solutions on Glass and

Plastic Surfaces, Anal. Chem., 3_7, 863-868 (1965).

28. A. E. Smith, A Study of the Variation with pH of the

Solubility and Stability of Some Metal Ions at Low

Concentrations in Aqueous Solution, Part II, Analyst,

98, 209-212 (1973).

29. Ibid., A Study of the Variation with pH of the

Solubility and Stability of Some Metal Ions at Low

Concentrations in Aqueous Solution, Part I, 98 , 65-68 (1973).

29a. H. A. Salman, Trace Element Analyses in Waters Combining Solvent Extraction with the Atomic Absorption

Microsampling Boat, Rept. Ch. E-102, Bureau of Reclamation, U. S. Department of the Interior, Denver, CO,

July 1969.

30. A. Rattonetti, Stability of Metal Ions in Aqueous

Environmental Samples, NBS, TS .

31. J. R. Moody, P. J. Paulsen, T. C. Rains, and H. L. Rook,

The Preparation and Certification of Trace Mercury in

Water Standard Reference Materials, NBS, TS .

32. J. M. Lo and C. M. Wai, Mercury Loss from Water During

Storage: Mechanisms and Prevention, Anal. Chem., 47 , 1869-1870 (1975).
33. C. Feldman, Preservation of Dilute Mercury Solutions,

Anal. Chem., 46, 99-102 (1974).

34. H. J. Issaq and W. L. Zielinski, Jr., Loss of Lead from

Aqueous Solution During Storage, Anal. Chem., 4_6, 1328-

1329 (1974).

35. P. Avotins and E. A. Jenne, The Time Stability of

Dissolved Mercury in Water Samples, J. Environ. Quality

(1975, in press)

.

36. C. W. Huey, F. Brinckman, W. Iverson, and S. 0. Grim,

Bacterial Volatilization of Cadmium, Proceedings of the

International Conference on Heavy Metals in the Environment, October 2731, 1975, Toronto (June 1976, in press)

.

37. S. E. Allen, H. M. Grimshaw, J. A. Parkinson, and C.

Quarmby, p. 99 in Chemical Analysis of Ecological

Materials, S. E. Allen, Ed. (Halstead Press), John

Wiley and Sons, New York (1974).

38. S. H. Harrison, P. D. LaFleur, and W. H. Zoller, Evaluation of Lyophilization, for the Preconcentration of

Natural Water Samples Prior to Neutron Activation

Analysis, Anal. Chem., 47, 1685-1688 (1975)

38a. R. H. Filby, K. R. Shah, and W. H. Funk, Role of Neutron

Activation Analysis in the Study of Heavy Metal Pollution of a Lake-River System, Proc. of the 2nd International Conference on Nuclear Methods in Environmental

Res., J. R. Vogt and W. Meyer, Ed., U. of Missouri,

Columbia, MO (1974)

.

39. J. Heron, Determination of Phosphate in Water After

Storage in Polyethylene, Limnol. Oceanogr., 7_, 316-321

(1962).

40. F. J. Philbert, The Effect of Sample Preservation by

Freezing Prior to Chemical Analysis of Great Lake

Waters, Proc. 16th Conf. Great Lakes Res., 282-293,

International Association Great Lakes Res. (1973).

41. E. C. Kuehner and D. H. Freeman, Containers for Pure

Substances, 297-306, in Purification of Inorganic and

Organic Materials, M. Zief, Ed., Marcel Dekker, New

York, NY (1969)

.

42. M. H. Bothner and D. E. Robertson, Mercury Contamination

of Sea Water Samples Stored in Polyethylene Containers,

Anal. Chem., 47, 592-595 (1975).

19
43. J. Moody, T. Rains, and M. Epstein (private communication) .

44. B. A. Malo and R. A. Baker, Cationic Concentration by

Freezing, in Trace Inorganics in Water, Advances in

Chemistry, Series 73, 149-163, Ed., R. F. Gould,

American Chemical Society, Washington, DC (1968).

45. K. K. S. Pillay, C. C. Thomas, Jr., J. A. Sondel, and

C. M. Hyche, Determination of Mercury in Biological and

Environmental Materials by Neutron Activation Analysis,

Anal. Chem., 4_3, 1419-1425 (1971).

46. P. D. LaFleur, Retention of Mercury When Freeze-Drying

Biological Materials, Anal. Chem., 4_5, 1534-1536 (1973).

47. J. S. Hislop and A. Parker, The Use of a Laser for

Cutting Bone Samples Prior to Chemical Analysis,

Analyst, _98, 694 (1973) .

48. J. R. Montgomery, S. E. Kolehmainen, M. D. Banus , B. J.

Bendien, J. L. Donaldson, and J. A. Ramirez, Individual

Variation of Trace Metal Content in Fish, NBS , TS .

49. J. Versieck, A. Speecke, J. Hoste, and F. Barbier,

Trace Contamination in Biopsies of the Liver, Clin.

Chem. , 19, 472-475 (1973)

50. G. L. Fisher, L. G. Davies, and L. S. Rosenblatt, The

Effects of Container Composition, Storage Duration, and

Temperature on Serum Mineral Levels, NBS, TS .

51. W. G. Walter, R. A. McBee, and K. L. Temple, Introduction

to Microbiology, D. Van Nostrand Co., NY (1973).

52. F. A. Ibbott, Sampling for Clinical Chemistry, NBS,

TS. *

53. S. H. Omang and 0. D. Vellar, Concentration Gradients

in Biological Samples During Storage, Freezing and

Thawing, Z. Anal. Chem., 2_69, 177-181 (1974).

54. V. T. Bowen and D. Sutton, Comparative Studies of

Mineral Constituents of Marine Sponges, Journal of

Marine Research, 1_0, 153-167 (1951).

55. R. H. Gibbs, Jr., E. Jarosewich, and H. L. Windom,

Heavy Metal Concentrations in Museum Fish Specimens:

Effects of Preservatives and Time, Science, 184 , 475-

477 (1974)

20
56. A. Cockburn, R. A. Barraco, T. A. Reymann, and W. H.

Peck, Autopsy of an Egyptian Mummy, Science, 187 , 1155-

1160 (1975).

57. R. G. Smith, Department of Environmental and Industrial

Health, University of Michigan, Ann Arbor, MI.

58. R. A. Kehoe, J. Res. Publ. Health Hyg . , 24, 1 (1961).

59. L. J. Goldwater, Mercury: A History of Quicksilver,

York, Baltimore (1972).

60. 0. J. Attoe, Potassium Fixation and Release in Soils

Occurring Under Moist and Drying Conditions, Soil Sci.

Soc. Proc, II, 145-149 (1946).

61. E. B. Schalscha, C. Gonzalez, I. Vergara, G. Galindo,

and A. Schatz, Effect of Drying on Volcanic Ash Soils

in Chile, Soil Sci. Soc. Proc, _2_9, 481-482 (1965).

62. N. J. Barrow, Studies on the Mineralization of Sulphur

from Soil Organic Matter, Aust. J. Agric. Res., 12 , 306-319 (1961).

63. M. I. Harpstead and B. L. Brage, Storage of Soil Samples

and Its Effect on the Subsequent Accumulation of Nitrate

Nitrogen During Controlled Incubation, Proc. Soil Sci.

Soc. Am., 2_2, 326-328 (1958).

64. H. F. Birch, The Effect of Soil Drying on Humus Decomposition and Nitrogen Availability, Plant and Soil, 10

,

9-30 (1958).

65. H. F. Birch, Further Observations on Humus, Decomposition and Nitrification, Plant and Soil, 11_, 262-286

(1959).

66. H. F. Birch, Nitrification in Soils After Different

Periods of Dryness, Plant and Soil, 12, 81-96 (1960).

67. Z. Nevo and J. Hagin, Changes Occurring in Soil Samples

During Air-Dry Storage, Soil Science, 102 , 157-160

(1966)

.

68. P. R. Hesse, p. 12 in A Textbook of Soil Chemical

Analysis, John Murray Publishers, Ltd., London (1971).

69. T. H. Arkely, D. N. Munns , and C M. Johnson, Preparation of Plant Tissues for Micronutrient Analysis:

Removal of Dust and Spray Contaminants, J. Agric. Food

Chem. , 8, 318-321 (1960)

.

21
70. J. V. Lagerwerff, Uptake of Cadmium, Lead, and Zinc by

Radish from Soil and Air, Soil Sci., Ill , 129-133

(1971)

71. D. E. Koeppe and R. J. Miller, p. 207 in Environmental

Pollution by Lead and Other Metals, Progress Rept. to

NSF-RANN, May 1971 - April 1972, Univ. of Illinois.

72. H. E. Bruce and S. P. Cram, Sampling Marine Organisms

and Sediments for High Precision Gas Chromatographic

Analysis of Aromatic Hydrocarbons, pp. 181-182 in

Marine Pollution Monitoring, Proc . of a Workshop held

at NBS, Gaithersburg, MD, NBS Spec. Publ. 409 (1974).

73. Federal Working Group on Pest Management, Guidelines on

Sampling and Statistical Methodologies for Ambient

Pesticide Monitoring, Washington, DC (1974).

73a. Ibid. (1975).

74. W. H. Lawrence, J. L. Mitchell, W. L. Guess, and J.

Autian, Toxicity of Plastics Used in Medical PracticeI, J. Pharm. Sciences, 5_2, 958-963 (1963).

75. J. Autian and A. J. Kapadia, The Leaching of a Constituent from Medical-Grade Plastic Tubings, Drug Std.,

2_8, 101-103 (1960).

76. G. W. Gibbs, Asbestos Contamination by Storage in

Polyethylene Bags, a report which is included in a paper accepted for publication by the American Industrial Hygiene Assoc. Journal.

77. A. J. Bauman, R. E. Cameron, G. Kritchevsky, and G.

Rouser, Detection of Phthalate Esters as Contaminants

of Lipid Extracts from Soil Samples Stored in Standard

Soil Bags, Lipids, 2, 85-86 (1967).

78. D. F. Goerlitz and E. Brown, Methods for the Analysis

of Organic Substances in Water, in Techniques of WaterResources Investigations, USGS Cat. #19:15/5: Bk 5,

Chap. A3 (1972)

79. C. S. Giam and H. S. Chan, Control of Blanks in the

Analysis of Phthalates in Air and Ocean Samples, NBS,

TS.*

80. C. S. Giam, H. S. Chan, and G. S. Neff, Sensitive

Method for Determination of Phthalate Ester Plasticizers

in Open-Ocean Biota Samples, Anal. Chem. , 4_7, 2225-

2229 (1975).

22
81. H. S. Hertz, S. N. Chesler, W. E. May, B. H. Gump, D.

P. Enagonio, and S. P. Cram, Methods for Trace Organic

Analysis in Sediments and Marine Organisms, pp. 197-199

in Marine Pollution Monitoring, Proc. of a Workshop

held at NBS, Gaithersburg , MD, NBS Spec. Publ. 409

(1974).

82. P. B. Hamilton and T. T. Myoda, Contamination of Distilled Water, HC1, and NH^OH with Amino Acids, Proteins, and Bacteria, Clin. Chem. , 2JD, 687-691 (1974).

83. M. S. Favero, L. A. Carson, W. W. Bond, and N. J.

Peterson, Pseudomonas aeruginosa : Growth in Distilled

Water from Hospitals, Science, r7_3, 836--838 (1971).

84. Y. Wolman and S. L. Miller, Amino Acid Contamination of

Aqueous Hydrochloric Acid, Nature, 234 , 548-549 (1971).

85. B. E. Conway, H. Angerstein-Kozlowska , W. B. A. Sharp,

and E. E. Criddle, Ultrapurif ication of Water for

Electrochemical and Surface Chemical Work by Catalytic

Pyrodistillation, Anal. Chem., 4_5, 1331-1336 (1973).

86. D. Straughan, Field Sampling Methods and Techniques for

Marine Organisms and Sediments, Marine Pollution Monitoring, Proc. of a Workshop held at NBS, Gaithersburg,

MD, NBS Spec. Publ. 409 (1974).

87. D. J. Jeffries and C. H. Walker, Uptake of pp'-DDT and

its Post-Mortem Breakdown in the Avian Liver, Nature,

212 , 533-534 (1966).

88. M. C. French and D. J. Jeffries, The Preservation of

Biological Tissue for Organochlorine Insecticide

Analysis, Bull, of Environ. Contam. and Tox., 6_, 460-

463 (1971).

89. D. Bristol, Effects of Storage Conditions on Residues

of 2,4-D and 2,4-DCP in Potatoes, NBS, TS.*

90. M. E. Zabik and L. Dugan, Jr., Potential of Freeze

Drying for Removal of Chlorinated Hydrocarbon Insecticides from Eggs, Jour. Food Sci., 3_6, 87-88 (1971).

90a. Robert J. Morris, The Preservation of Some Oceanic

Animals for Lipid Analyses, J. Fish. Res. Board Canada,

2_9, 1303-1307 (1972).

91. D. Smith, Influence of Drying and Storage Conditions on

Nonstructural Carbohydrate Analysis of Herbage Tissue - A Review, J. Br. Grassld. Soc. , 2_8, 129-134 (1973).

23
92. L. F. Molloy, D. J. Giltrap, T. W. Collie, and A. J.

Metson, Degradation of Higher Fatty Acids in Perennial

Rye Grass and White Clover Following Drying and Storage,

J. Sci. Food and Agric, 2_5, 595-606 (1974).

93. W. P. Iverson, Private Communication.

94. S. Fleischer and M. Kervina, Long-Term Preservation of

Liver for Subcellular Fractionation, Methods in

Enzymology, 31, Pt. A, 3-6 (1974).

94a. D. W. McPeak and F. R. Camp, Jr., Frozen Blood Shipping,

Military Medicine, 14_0, 468-470 (1975).

95. C. R. Valeri, A. H. Runck, and L. E. McCallum, Observations on Autologous, Previously Frozen, Deglycerolyzed,

Agglomerated Resuspended Red Cells. I. Effect of

Storage Temperatures. II. Effect of Adenine Supplementation of Glycerolized Red Cells Prior to Freezing,

Transfusion, 7, 105-116 (1967).

96. H. T. Meryman and M. Hornblower, A Method for Freezing

and Washing Red Blood Cells Using a High Glycerol

Concentration, Transfusion, 1_2, 145-156 (1972) .

97. J. G. Gibson, J. L. Tullis, R. J. Tinch, W. R. Ryan,

and S. Diforte, The Post-Thaw Viability of ACD and CPD

Blood Preserved in the Frozen State With and Without

Added Adenine, Transfusion, 12, 198-207 (1972).

98. J. Farrant, S. C. Knight, L. E. McGann, J. O'Brien,

Optimal Recovery of Lymphocytes and Tissue Culture

Cells Following Rapid Cooling, Nature, 24_9, 452-453

(1974) .

ITSymposium on Accuracy in Trace Analysis: Sampling, Sample

Handling, and Analysis, Proc. of the 7th IMR Symp .

P. D. LaFleur, Ed., NBS Special Publ. 422 (in press, 1975)

24
Bibliography Addendum A - Microbiologicals

A-l W. M. Abbott and J. S. Hembree, Absence of Antigenicity

in Freeze-Dryed Skin Allografts, Cryobiol., 6_, 416-418

(1970)

.

A-2 M. D. Alur and N. Grecz, Mechanism of Injury of

Escherichia coli by Freezing and Thawing, Biochem. and

Biophys. Res. Commun., 62, 308-312 (1975).

A-3 H. Bank, Freezing Injury in Tissue Cultured Cells as Visualized by Freeze-Etching , Exptl. Cell Res., 85,

367-376 (1974).

A-4 J. B. Bateman, P. A. McCaffrey, R. J. O'Connor, and G.

W. Monk, Relative Humidity and the Killing of Bacteria,

Appl. Microbiol., 6, 567-571 (1961).

A-5 S. Berman, P. L. Altieri, A. Groffinger, and J. P.

Lowenthal, Freeze Drying Various Attenuated Strains of

Pasteurella Pestis , Cryobiol., 7, 40-43 (1970).

A-6 S. Berman, P. L. Altieri, A. Groffinger, J. P. Lowenthal,

and S. B. Formal, Freeze Drying Various Strains of

Shigella , Appl. Microbiol., 1_6, 1779-1781 (1968).

A-7 H. L. Braid, R. F. Hagerty, and W. H. Lee, Jr., Preservation of Cellular Viability of Human Cartilage at

Low Temperature, Transpl., 4, 94-99 (1966).

A-8 B. L. Brown, S. C. Nagle, Jr., J. D. Lehmann, and C. D.

Rapp, Preservation of Insect Cells in Liquid Nitrogen,

Tech. Manuscript 590, Dept. of the Army, Fort Detrick,

Frederick, MD (1970)

.

A-9 B. L. Brown, S. C. Nagle, Jr., J. D. Lehmann, and C. D.

Rapp, Storage of Aedes Aegypti and Aedes Albopictus

Cells Under Liquid Nitrogen, Cryobiol., 7_, 249-251

(1971).

A-10 M. S. Brown and F. W. Reuter, Freezing of Nonwoody

Plant Tissues. III. Videotape Micrography and the

Correlation between Individual Cellular Freezing Events

and Temperature Changes in the Surrounding Tissue,

Cryobiol., 11, 185-191 (1974).

A-ll W. Briischweller and W. Gehring, A Method for Freezing

Living Ovaries of Drosophila melanogaster Larvae and

Its Application to the Storage of Mutant Stocks,

Separatum Experientia, 2_9, 135 (1973) .

25
A-12 W. A. Cassel and K. M. McCaskill, Ehrlich Ascites

Tumor Preservation for 15 Years - A Simple Method,

Appl. Microbiol., 2_8, 726 (1974).

A-13 W. H. J. Crombach, Deep-Freezing of Bacterial DNA for

Thermal Denaturation and Hybridization Experiments,

J. Microbiol, and Serology, 39, 249-255 (1973).

A-14 R. Digirolamo, J. Liston, and J. Matches, The Effects

of Freezing on the Survival of Salmonella and E. coli

in Pacific Oysters, J. Food Sci., 3_5, 13-16 (1970]T

A-15 J. Farrant, Mechanism of Cell Damage During Freezing

and Thawing and its Prevention, Nature, 205 , 1284-

1287 (1965).

A-16 J. Farrant, S. Knight, L. E. McGann, J. O'Brien,

Optimal Recovery of Lymphocytes and Tissue Cells

Following Rapid Cooling, Nature, 249 , 452-453 (1974).

A-17 W. N. Fishbein, Mechanism of Freezing Damage to Mouse

Liver Using a Mitochondrial Enzyme Assay. III. Cryophyllaxis with DMSO and Enzyme Localization, Cryobiol.,

8, 293-299 (1971).

A-18 W. N. Fishbein and R. E. Stowell, Studies of the

Mechanism of Freezing Damage to Mouse Liver Using a Mitochondrial Enzyme Assay, I. Temporal Localization of

the Injury Phase During Slow Freezing, Cryobiol., 4_, 283-289 (1968).

A-19 Ibid , II. Comparison of Slow and Rapid Cooling Rates,

6, 227-234 (1969).

A-20 M. P. Garber and P. L. Steponkus, Alterations in

Chloroplast Membranes during Cold Acclimation and

Freezing, Cryobiol., 1_0, 532 (1973).

A-21 L. J. Goatcher, S. E. Engler, D. C. Wagner, and

D. C. Westhoff, Effect of Storage at 5°C on Survival

of Vibrio Parahemolyticus in Processed Maryland

Oysters, J. Milk Food Tech. , 3_7, 74-77 (1974).

A-22 R. Gomez, M. Takano, and A. J. Sinskey, Characteristics

of Freeze-Dried Cells, Cryobiol., 1_0, 368-374 (1973).

A-23 E. Griffiths and H. F. Birch, Microbiological Changes

in Freshly Moistened Soil, Nature, 189, 424 (1961).

26
A-24 D. F. Hiltz, L. J. Bishop, and W. J. Dyer, Accelerated

Nucleotide Degradation and Glycolysis During Warming

to and Subsequent Storage at -5°C of Prerigor, QuickFrozen Adductor Muscle of the Sea Scallop ( Placopecten

magillanicus ), J. Fish Res. Board of Canada^ 31

,

1181-1187 (1974)

.

A-25 International Atomic Energy Agency, Reference Methods

for Marine Radioactivity Studies, Tech. Rept. Series

118, IAEA, Vienna, pp. 26, 28 (1970).

A-26 E. Israeli and A. Kohn, Protection of Lyophilized E.

coli by Colicin El Treatment, FEBS Letters, 2_6, 323-

326 (1972).

A-27 E. Israeli, A. Kohn, and J. Gitelman, The Molecular

Nature of Damage by Oxygen to Freeze-Dried Escherichia

coli , Cryobiol., 1_2, 15-25 (1975).

A-28 D. W. Janssen and F. F. Busta, Influence of Milk

Components on the Injury, Repair of Injury and Death

of Salmonella anatum Cells Subjected to Freezing and

Thawing, Appl. Microbiol., ^6, 725-732 (1973).

A-29 B. Kirsop, The Stability of Biochemical, Morphological

and Brewing Properties of Yeast Cultures Maintained

by Subculturing and Freeze-Drying, J. Inst, of Brew.

(London), 8_0, 565-570 (1974).

A-30 M. Kuzminska, A. Szdlowski, I. Werner, and L. Obrzut,

Microbiological Analysis of Fish Dishes During Freezing

and Subsequent Cold Storage at -22°C, International

Institute of Refrigeration, 1972 , 123-132.

A-31 K. A. Lehner, Freezing Preservation of Foods with

Carbon Dioxide and Dry Ice, Amer . Soc. Heat. Refrig.

Air Cond. Eng. J., 13, 41-43 (1971).

A-32 J. Lundy and W. G. Fitz-William, A Portable Dry-Ice

Storage Chamber for Enhanced Preservation of Enzymes

in Frozen Tissue Specimens, Stain Tech., 4_6, 259-261

(1971)

.

A-33 G. M. Martin, A Case for Regional Culture Collections

of Microorganisms, Nature, 247 , 431-433 (1974).

A-34 T. Matsuhashi, Studies on Freezing and Drying of

Agar Gel, Refrig., 49, 966-973 (1974).

27
A-35 D. E. McComb and C. I. Puzniak, Micro Cell Culture

Method for Isolation of Chlamydia trachomatis , Appl.

Microbiol., 2_8, 727-729 (1974).

A-36 J. Nath and J. 0. Anderson, Some Biochemical Alterations

Associated with the Freeze Preservation of Pollen,

Cryobiol., 10, 533 (1973).

A-37 0. Novick, E. Israeli, and A. Kohn, Nucleic Acid and

Protein Synthesis in Reconstituted Lyophilized

Escherichia coli Exposed to Air, J. Appl. Bact.,

35, 185-191 (1972).

A-38 K. Ostrowski, Current Problems of Tissue Banking,

Transpl. Proc . , 1, 126-131 (1969).

A-39 W. Partmann, Some Effects of Defined Conditions of

Freezing and Thawing on Histological Changes in White

Muscle of Carp, International Inst, of Refrig.,

1972 , 77-84.

A-40 F. F. G. Rommerts, L. G. van Doom, H. Galjaard,

B. A. Cook, and H. J. van der Molen, Dissection of

Wet Tissue and of Freeze-Dried Sections in the

Investigation of Seminferous Tubules and Interstitial

Tissue from Rat Testis, J. Histochem. and Cytochem.

,

21, 572-579 (1973).

A-41 V. U. Schneider, J. Hahn, and H. Sulzer, Preliminary

Results of Low Temperature Preservation in Mouse and

Rabbit Ova, Dtsch. Tierarztl. Wschr., 8_1, 470-472 (1974)

A-42 T. H. Scholten and J. Yang, Evaluation of Unpreserved

and Preserved Stools for the Detection and Identification

of Parasites, Amer. J. of Clin. Path., 62_, 563-567 (1974)

A-43 K. W. Sell, Viability Assay of Organized Tissues and

Organs, Cryobiol., 4, 133-135 (1967).

A-44 E. M. Simon and M. V. Schneller, The Preservation of

Ciliated Protozoa at Low Temperature, Cryobiol., 10 , 421-426 (1973).

A-45 R. B. Smittle, S. E. Gilliland, and M. L. Speck,

Death of Lactobacillus bulgar icus Resulting from

Liquid Nitrogen Freezing, Appl. Microbiol., 24_, 551-

554 (1972).

A-46 J. Stadhousers, G. Hup, and L. A. Jansen, A Study of

the Optimum Conditions of Freezing and Storing Concentrated Mesophilic Starters, Neth. Milk Dairy J., 25 , 229-239 (1971).

L O
P. L. Steponkus and S. C. Wiest, Freezing Injury of

Plant Plasma Membranes, Cryobiol., 1_0, 532 (1973).

M. Suzuki, Stability and Residual Moisture Content of

Dried Vaccinia Virus, Cryobiol., 1_0, 432-434 (1973).

Ibid . Protectants in the Freeze-Drying and the

Preservation of Vaccinia Virus, 435-439.

M. Takano, J. Sado, T. Ogawa, and G. Terui, Freezing

and Drying of Spirulina platensis , Cryobiol., 10 , 440-444 (1973).

A-51 R. Todorova, On the Lyophilization of Viruses and

Virus Vaccines, Vet. Med. Nauki, Sofia, 1_0, 52-53,

(1973) .

L. E. Towill, P. Mazur, and G. P. Howland, Plasmolysis

Injury as a Factor in Freezing Injury in Plant Tissue

Culture, Cryobiol., 1_0, 532 (1973).

A-53 S. Tsuru, Preservation of Marine and Fresh Water Algae

by Means of Freezing and Freeze Drying, Cryobiol.,

10, 445-452 (1973).

A-54 S. Tsuru, Protection Mechanisms of Biological Materials

During Freezing and Thawing, (Fermentation Research

Institute, Agency of Industrial Science and Technology)

,

97-102, I . I. F. -I.I. R. -Commission Cl-Sappors, 1973-5.

A-55 K. J. Whittle, A Multiple Sampling Technique for Use

with the Cell-Fragility Method of Determining

Deteriorative Changes in Frozen Fish, J. Sci. Fd.

Agric, 24, 1383-1389 (1973).

G. L. Zink and H. C. Hines, The Freezing and Preservation of Bovine Erythrocytes in Liquid Nitrogen, Anim.

Blood Grps. biochem. Genet., 1, 23-32 (1970).

29
Bibliography Addendum B - Blood

B-l J. Abramowitz, A. Stracher, and T. C. Detwiler,

Proteolysis of Myosin during Platelet Storage, J. Clin.

Investig., 53, 1493-1496 (1974).

o B-2 0. Akerblom and C. F. Hogman, Frozen Blood: A Method

for Low-Glycerol , Liquid Nitrogen Freezing Allowing

Different Post-Thaw Deglycerolization Procedures,

Transf . , 14, 16-26 (1974)

B-3 H. Chaplin, Jr., E. Beutler, J. A. Collins, E. R.

Giblett, and H. F. Polesky, Current Status of Red-Cell

Preservation and Availability in Relation to the Developing National Blood Policy, New Eng . J. Med., 291 , 68-74 (1974).

B-4 D. G. Corby, K. A. Preston, and T. P. O'Barr, Adverse

Effect of Gel Filtration on the Function of Human

Platelets, Proc. Soc. Exptl. Biol, and Med., 146 , 96-98

(1974).

B-5 J. P. Crowley, E. M. Skrabut, and C. R. Valeri, Immunocompetent Lymphocytes in Previously Frozen Washed Red

Cells, Vox Sang., 2_6, 513-517 (1974).

B-6 E. Dobry, J. Fiala, and J. Livora, A Comparison of the

Cryoprotective Effect of Glycerol and Dimethyl Sulfoxide

in the Preservation of Murine Bone Marrow, Blut Zeitschr

Gesamte Blut., 2_3, 359-362 (1971).

B-7 J. R. Geraci and F. R. Engelhardt, The Effects of

Storage Time, Temperature, and Anticoagulants on Harp

Seal, Phoca Groenlandica Hemograms: A Simulated Field

Study, Physiol. Zool., 47_, 22-28 (1974).

B-8 M. Hills, G. I. C. Ingram, and M. 0. Matchett, Lyophilized Plasma as an Assay Standard for Factor VIII:

Calibration and Control with Fresh Plasma Samples,

Brit. J. Haemat., 1_8, 617-624 (1970).

B-9 M. S. Jacobson, R. Parkman, L. N. Button, R. J. Jaeger,

and S. V. Kevy, The Toxicity of Human Serum Stored in

Flexible Polyvinyl Chloride Containers on Human

Fibroblast Cell Cultures: An Effect of Di- 2-Ethylhexyl

Phthalate, Res. Commun. Chem. Path, and Pharmacol., 9_, 315-323 (1974).

30
B-10 S. M. Lewis and C. T. H. Stoddart, Effects of Anticoagulents and Containers (Glass and Plastic) on the

Blood Count, Lab. Prac, 2_0, 787-792 (1971).

B-ll S. Murphy, S. N. Sayar, N. L. Abdou, and F. H. Gardner,

Platelet Preservation by Freezing. Use of Dimethylsulfoxide as Cryoprotective Agent, Transf., 1_4_, 139-

144 (1974).

B-12 J. Niedworok, Comparative Investigations of Plasma

Lipids during the Blood Preservation at Ultra-Low

Temperatures in Relation to the Preservative, Acta

Haemat. Pol., 2, 172-173 (1971).

B-13 V. S. Seidl, Tiefkiihlkonservierung von Blut, Blut

Zeitschr. Gesamte Blut., 2_5, 145-149 (1972).

B-14 L. Weatherbee, H. H. Spencer, C. T. Knorpp, S. M.

Lindenauer, P. W. Gikas, and N. W. Thompson, Coagulation Studies after Transfusion of Hydroxyethyl

Starch Protected Frozen Blood in Primates, Transf.,

14, 109-115 (1974).

B-15 F. C. Wessling and P. L. Blackshear, The Effect of

Gases on the Recovery of Human Red Blood Cells,

Cryobiol., 7, 265-273 (1971).

B-16 A. E. Woolgar, Hemolysis of Human Red Blood Cells by

Freezing and Thawing in Solutions Containing Polyvinylpyrrolidone: Relationship with Posthypertonic

Hemolysis and Solute Movements, Cryobiol., 11 , 52-59

(1974).

31
Bibliography Addendum C - Biological Sample

Preparation and Storage

C-l A. Abu-Samra, J. S. Morris, and S. R. Koirtyohann,

Wet Ashing of Some Biological Samples in a Microwave

Oven, Anal. Chem. , 4_7, 1475-1477 (1975).

C-2 D. Behne and P. A. Matamba, Drying and Ashing of Biological Samples in the Trace Element Determination by

Neutron Activation Analysis, Z. Anal. Chem., 274 , 195-

197 (1975)

C-3 F. R. Camp, F. R. Ellis, C. E. Shields, and M. M. Werline

Long-Term Preservation of Biologicals for the Forensic

Laboratory and Their Areas of Application, J. Forensic

Sci. , 13, 419-432 (1968)

C-4 J. Chirife and M. Karel, Contribution of Adsorption to

Volatile Retention in a Freeze-Dried Food Model Containing PVP, J. Food Science, 38, 768-771 (1973).

C-5 J. Chirife and M. Karel, Volatile Retention During

Freeze Drying of Protein Solutions, Cryobiol., 11 , 107-115 (1974).

C-6 I. Y. Donev, Rapid Homogenization and Drying of

Biological Material, in Accuracy in Trace Analysis:

Sampling, Sample Handling, and Analysis, Proc. of

the 7th IMR Symp . , P. D. LaFleur, Ed., NBS Spec.

Publ. 422 (in press 1975).

C-7 N. El Bassam and F. Mertens, Influence of Various

Storage and Drying Methods on the Chemical Composition

of Sludge, Landbauforsch. Voelkenrode, 2_2, 41-44 (1972).

C-8 J. Flink and M. Karel, Effects of Process Variables on

Retention of Volatiles in Freeze-Drying , J. Food Sci.,

3_5, 444-447 (1970).

C-9 J. M. Flink and T. P. Labuza, Retention of 2-Propanol

at Low Concentration by Freeze-Drying Carbohydrate

Solutions, J. Food Sci., 37, 617-618 (1972).

C-10 R. Gomez, M. Takano, and A. J. Sinskey, Characteristics

of Freeze-Dried Cells, Cryobiology, 1_0, 368-374 (1973).

C-ll T. T. Gorsuch, Dissolution of Organic Materials,

in Accuracy in Trace Analysis: Sampling, Sample

Handling, and Analysis, Proc. of the 7th Symp.,

P. D. LaFleur, Ed., NBS Spec. Publ. 422 (in press

1975) . 32
C-12 T. T. Gorsuch, The Destruction of Organic Matter,

Pergamon Press, Oxford, New York, Toronto, Sydney

(1970).

C-13 G. J. Haas, S. Barnett, and H. E. Prescott, Jr.,

Pressure-Freezing -- A New Pretreatment Process to

Prevent Shrivelling during Drying of Cellular Foods,

in part in Cryobiol., 9_, 101-106 (1972) and in part

in J. Food Sci. , 37 (1972)

.

C-14 R. Hamm, K. Potthast, and L. Acker, Influence of Water

Activity on Enzymatic Changes in Freeze-Dehydrated

Muscle. I. The Breakdown of Adenosine Triphosphate,

Z. Lebensm. Unters . -Forsch. , 1_54, 73-79 (1974).

C-15 J. A. Hesek and R. C. Wilson, Use of Microwave Oven

in In-Process Control, Anal. Chem. , 46, 1160 (1974).

C-16 C. S. Huber, R. B. Harrington, and W. J. Stadelman,

Effect of Freezing Rate and Freeze-Drying on the

Soluble Proteins of Muscle. II. Turkey Muscle,

J. Food Sci., 35, 233-236 (1970).

C-17 C. S. Huber and W. J. Stadelman, Effect of Freezing

Rate and Freeze-Drying on the Soluble Proteins of

Muscle. I. Chicken Muscle, J. of Food Sci., 35 , 229-232 (1970).

C-18 B. M. Kilcullen and R. D. Harter, A Simple System

for Freeze Drying, J. Chem. Ed., _5_1, 590 (1974).

C-19 B. J. Longan, G. A. Hruzek, and E. E. Burns, Effect

of Processing Variables on Volatile Retention of

Freeze-Dried Carrots, J. Food Science, 3_9, 1191-1194

(1974)

.

C-20 H. A. Massaldi and C. J. King, Volatiles Retention

During Freeze-Drying of Synthetic Emulsion, J. Food

Sci. , 39, 438-444 (1974)

.

C-21 J. Parker and H. M. Smith, Design and Construction of

a Freeze Dryer Incorporating Improved Standards of

Biological Safety, J. Appl. Chem. Biotechnol., 22 , 925-932 (1972).

C-22 H. Souzu, The Phospholipid Degradation and Cellular

Death Caused by Freeze-Thawing or Freeze-Drying of

Yeast, Cryobiol., 10/ 427-431 (1973).

C-23 L. U. Thompson and 0. Fennema, Effect of Freezing

on Oxidation of L-Ascorbic Acid, J. Agric. Food Chem.,

19, 121-124 (1971).

33
C-24 J, M. Tuomy, Freeze-Drying of Foods for the Armed

Services, Tech. Rept. 72-28-FL, U. S. Army Natick Lab.,

Natick, Mass. (1971)

C-25 V. L. Voznesenskii and L. A. Filippova, Instrument for

Freeze-Drying Tissues, Soviet Plant Physiol., 16 , 793-794 (1969).

C-26 J. W. Young and G. D. Christian, Simple Inexpensive

Freeze-Drying Procedure, Anal. Chem. , 45, 1296 (1973).

Acknowledgment

This work was supported in part by the Environmental

Protection Agency under the Interagency Agreement No. EPA1AG-D5-0568.

Note:

Certain Trade names and company names are used in this paper,

In no case does such identification imply recommendation or endorsement by the National Bureau of Standards.

34
NBS-114A (REV. 7-731

U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBS TN-9292. Gov't Accession

No.

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

A Survey of Current Literature on Sampling, Sample

Handling, and Long Term Storage for Environmental

Materials

5. Publication Date October 1976

6. Performing Organization Code

7. AUTHOR(S) F, . J . Maienthal and D . A . Becker8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

Same as 9.

13. Type of Report & Period Covered Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

To be submitted to Analytical Chemistry

16. ABSTRACT (A 200-word or less factual summary ot most significant information. If document includes a significant bibliography or literature survey, mention it here.)

This article is the result of an extensive literature survey

to establish optimum sampling, sample handling and long term

storage techniques for a wide variety of environmental samples,

to retain sample integrity. The components of interest in these

samples are trace elements, organics , pesticides, radionuclides

or microbiologicals . This survey was done both manually and

by use of various bibliographical retrieval services. Also

the advice and opinions of workers in various aspects of

the fields was obtained.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons) Environmental samples; Long-term storage;

Microbiologicals; Organics; Pesticides; Sample handling; Sampling;

Chemical analysis; Radionuclides; Trace Elements

18. AVAILABILITY |

' Unlimited

I For Official Distribution. Do Not Release to NTIS

I -X 1 Order From Sup. of Doc, U.S. Government Printine X)fiice Washington, D.C. 20402, SD Cat. No. C13 . 46:929

I

! Order From National Technical Information Service (NTIS)

Springfield, Virginia 22151

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF PAGES

40

22. Price $0.85

USCOMM-DC 29042-P74


SINGLE

CRYSTAL

DATA

REVISED! UPDATED!

In 1954, the first edition of CRYSTAL DATA (Determinative Tables

and Systematic Tables) was published as Memoir 60 of the Geological Society of America. In I960,

the second edition of the Determinative Tables was issued as Monograph

5 of the American Crystallographic

Association, and in 1967, the Systematic Tables were issued as Monograph 6. These editions proved ex- tremely valuable to crystallographers

throughout the world. Recognizing the need for updated crystallographic in- formation, the National Bureau of Standards Office of Standard Reference Data has sponsored the issuance of a new

edition.

This, the THIRD EDITION, should be of particular interest not only to crystallographers but also to chemists, minera

ogists, physicists and individuals in related fields of study. The current edition,

which comprises two volumes, Organic and

Inorganic, is a thoroughly revised and up- dated work, containing over 25,000 entries. The entries are listed, within each crystal sys- tem, according to increasing values of a determinative number: a/b ratio in trimetric systems, c/a ratio in dimetric systems, and

cubic cell edge a, in the isometric system. In addition, the following information is given: INORGANIC VOLUME $50.00 ORGANIC VOLUME $30.00

axial ratio(s) and interaxial angles

not fixed by symmetry, cell dimensions, space group or diffraction aspect, number of formula units per unit cell, crystal structure, (whether determined), measured

density and x-ray calculated density. Also listed is the name of the compound and synonym(s)

chemical formula, literature ref erence and transformation

matrix. When available, the crys

tal structure type, crystal habit cleavages, twinning, color, optical

properties, indices of refraction

optical orientation, melting point

and transition point are also

listed. THIS EDITION culminates years of

effort by J. D. H. Donnay, Johns

Hopkins University, Helen M. Ondik,

National Bureau of Standards, Sten Samson, California Institute of Technology, Quintin Johnson, Lawrence Radiation Laboratory,

Melvin H. Mueller, Argonne National

Laboratory, Gerard M. Wolten, Aero- space Corporation, Mary E. Mrose,

U.S. Geological Survey, Olga Ken- nard and David G. Watson, Cambridge University, England and

Murray Vernon King, Massachusetts General Hospital.

Plus shipping and handling

Shipments are made via insured parcel post. Additional charges for shipments by air or commercial carrier. TERMS: Domestic—30 days Foreign—prepayment required. Address all orders to: JOINT COMMITTEE ON POWDER DIFFRACTION STANDARDS 1601 Park Lane, Swarthmore, Pennsylvania 19081

Please accept my order for CRYSTAL DATA, DETERMINATIVE TABLES, Third Edition, Donnay/Ondik.

D Organic Volume D Inorganic Volume

Ship to:

Signature _^^_____ jCPDb
NBS TECHNICAL PUBLICATIONS

PERIODICALS JOURNAL OF RESEARCH reports National Bureau

of Standards research and development in physics,

mathematics, and chemistry. It is published in two

sections, available separately:

• Physics and Chemistry (Section A)

Papers of interest primarily to scientists working in these fields. This section covers a broad range of physical and chemical research, with major emphasis on

standards of physical measurement, fundamental constants, and properties of matter. Issued six times a year. Annual subscription: Domestic, $17.00; Foreign, $21.25. • Mathematical Sciences (Section B)

Studies and compilations designed mainly for the mathematician and theoretical physicist. Topics in mathematical statistics, theory of experiment design, numerical

analysis, theoretical physics and chemistry, logical de- sign and programming of computers and computer sys- tems. Short numerical tables. Issued quarterly. Annual

subscription: Domestic, $9.00; Foreign, $11.25.

DIMENSIONS/NBS (formerly Technical News Bulletin) —This monthly magazine is published to inform

scientists, engineers, businessmen, industry, teachers,

students, and consumers of the latest advances in science and technology, with primary emphasis on the work at NBS. The magazine highlights and reviews

such issues as energy research, fire protection, building

technology, metric conversion, pollution abatement,

health and safety, and consumer product performance.

In addition, it reports the results of Bureau programs

in measurement standards and techniques, properties of matter and materials, engineering standards and services, instrumentation, and automatic data processing.

Annual subscription: Domestic, $9.45; Foreign, $11.85.

N0NPERI00ICALS

Monographs—Major contributions to the technical liter- ature on various subjects related to the Bureau's scientific and technical activities. Handbooks—Recommended codes of engineering and

industrial practice (including safety codes) developed

in cooperation with interested industries, professional

organizations, and regulatory bodies. Special Publications—Include proceedings of conferences sponsored by NBS, NBS annual reports, and other

special publications appropriate to this grouping such

as wall charts, pocket cards, and bibliographies.

Applied Mathematics Series—Mathematical tables, manuals, and studies of special interest to physicists, engineers, chemists, biologists, mathematicians, computer programmers, and others engaged in scientific and technical work.

National Standard Reference Data Series—Provides

quantitative data on the physical and chemical properties of materials, compiled from the world's literature and critically evaluated. Developed under a world-wide

program coordinated by NBS. Program under authority

of National Standard Data Act (Public Law 90-396).

NOTE: At present the principal publication outlet for these data is the Journal of Physical and Chemical

Reference Data (JPCRD) published quarterly for NBS

by the American Chemical Society (ACS) and the American Institute of Physics (AIP). Subscriptions, reprints,

and supplements available from ACS, 1155 Sixteenth

St. N.W., Wash. D. C. 20056. Building Science Series—Disseminates technical infor- mation developed at the Bureau on building materials,

components, systems, and whole structures. The series presents research results, test methods, and performance criteria related to the structural and environmental

functions and the durability and safety characteristics

of building elements and systems.

Technical Notes—Studies or reports which are complete

in themselves but restrictive in their treatment of a

subject. Analogous to monographs but not so comprehensive in scope or definitive in treatment of the subject area. Often serve as a vehicle for final reports of work performed at NBS under the sponsorship of other government agencies.

Voluntary Product Standards—Developed under proce- dures published by the Department of Commerce in Part

10, Title 15, of the Code of Federal Regulations. The

purpose of the standards is to establish nationally rec- ognized requirements for products, and to provide all concerned interests with a basis for common under- standing of the characteristics of the products. NBS

administers this program as a supplement to the activities of the private sector standardizing organizations.

Consumer Information Series—Practical information, based on NBS research and experience, covering areas

of interest to the consumer. Easily understandable lang- uage and illustrations provide useful background knowledge for shopping in today's technological marketplace.

Order above NBS publications from: Superintendent

of Documents, Government Printing Office, Washington,

D.C. -20402. Order following NBS publications—NBSIR's and FIPS

from the National Technical Information Services,

Springfield, Va. 22161. Federal Information Processing Standards Publications (FIPS PUBS)—Publications in this series collectively constitute the Federal Information Processing Standards Register. Register serves as the official source of information in the Federal Government regarding stand- ards issued by NBS pursuant to the Federal Property

and Administrative Services Act of 1949 as amended,

Public Law 89-306 (79 Stat. 1127), and as implemented

by Executive Order 11717 (38 FR 12315, dated May 11, 1973) and Part 6 of Title 15 CFR (Code of Federal

Regulations).

NBS Interagency Reports (NBSIR)—A special series of interim or final reports on work performed by NBS for

outside sponsors (both government and non-government). In general, initial distribution is handled by the sponsor; public distribution is by the National Technical Information Services (Springfield, Va. 22161) in paper copy or microfiche form.

BIBLIOGRAPHIC SUBSCRIPTION SERVICES

The following current-awareness and literature-survey

bibliographies are issued periodically by the Bureau:

Cryogenic Data Center Current Awareness Service. A

literature survey issued biweekly. Annual subscription: Domestic, $20.00; Foreign, $25.00.

Liquified Natural Gas. A literature survey issued quarterly. Annual subscription: $20.00.

Superconducting Devices and Materials. A literature survey issued quarterly. Annual subscription: $20.00.

Send subscription orders and remittances for the pre- ceding bibliographic services to National Bureau of Standards, Cryogenic Data Center (275.02) Boulder,

Colorado 80302.
U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington, DC. 20234

OFFICIAL BUSINESS

Penalty for Private Use. $300

POSTAGE AND FEES PAID

U.S. DEPARTMENT OF COMMERCE COM-215

SPECIAL FOURTH-CLASS RATE BOOK

U.S.I

^~%%. *!&> YEARS

1901-1376

^e-1916
9S9&M

SB

He

9'NflS MB

ganxnBn

' HI

wfffflWfil

B

Bfl! he

w

w>

91

HDH

EftaBSfim

BrailSB

M wjajaiMj

B

BhbHHhb^B

u-Xfl

^11

Lit

rB

JET!HI IaXHI

B B B

OR W| BHbD B Y

nf>^

hni

-cainote929

| sa^ey

W&
*-*X* m&A